Fogged,direct positive silver halide emulsions containing hydroxyphthalein dyes and sulfonated compounds

ABSTRACT

A DIRECT POSITIVE SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING AT LEAST ONE DYE REPRESENTED BY THE GENERAL FORMULA:   3-(O=),6-((-)O-),9-(2-((-)OOC-),(X5)Q-PHENYL),(X1)M,(X2)N,   (X4)P,(X3)L-3H-XANTHENE   WHEREIN X1, X2, X3, X4 AND X5 EACH REPRESENTS A HALOGEN ATOM, M, N, L, AND P REPRESENT 0 OR 1, Q REPRESENTS 0, 1. 2, 3 OR 4, PROVIDING THAT WHEN SAID M, N, L, P AND Q ARE 0, SAID X1, X2, X3, X4 AND X5 EACH REPRESENTS A HYDROGEN ATOM, AND M REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, AN ALKALI METAL ATOM, NH4, AND AN ALKALINE EARTH METAL, TOGETHER WITH AT LEAST ONE COMPOUND REPRESENTED BY THE GENERAL FORMULA:   (-N=C(-R1)-Y=C(-R2)-N=)&gt;C-NH-A-NH-C&lt;(-N=C(-R3)-Y=C(-R4)-   N=)   WHEREIN Y REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF =CH- AND =N-, R1, R2, R3, AND R4 EACH REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, A HYDROXYL GROUP AN ALKOXYL GROUP, AN ARYLOXYL GROUP, A HALOGEN ATOM, A HETEROCYCLIC NUCLEUS, AN ALKYLTHIO GROUP, A HETEROCYCLYTHIO GROUP, AN ARYLTHIO GROUP, AN AMINO GROUP, AN ALKYLAMINO GROUP, A SUBSTITUTED ALKYLAMINO GROUP, AN ARYLAMINO GROUP, A SUBSTITUTED ARYLAMINO GROUP, A HETEROCYCLYLAMINO GROUP, AN ARYL GROUP AND A MERCAPTO GROUP, AND -A- REPRESENTS AT LEAST ONE MEMBER DEFINED AS A1 AND A2, SAID A1 BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF:   -(3-(M-O3S-)-1,4-PHENYLENE)-CH=CH-(2-(M-O3S-)-1,4-PHENYL-   ENE)-, -(2,6&#39;&#39;-DI(M-O3S-)-4,4&#39;&#39;-BIPHENYLENE)-, -((1,4-   PHENYLENE)-CO-NH-(3-(M-O3S-)-1,4-PHENYLENE))2-CH=CH-,   -(3-(M-O3S-)-1,4-PHENYLENE)-S-(2-(M-O3S-)-1,4-PHENYLENE)-,   -(3-(M-O3S-)-1,4-PHENYLENE)-CH2-CH2-(2-(M-O3S-)-1,4-PHENYL-   ENE)-, AND -(3-(M-O3S-)-1,4-PHENYLENE)-C*C-(2-(M-O3S-)-   1,4-PHENYLENE)-   WHEREIN M REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM AND A CATION GIVING WATER SOLUBILITY TO SAID COMPOUND, AND SAID A2 BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF:   -(4,4&#39;&#39;-BIPHENYLENE)-, -(1,4-PHENYLENE)-, -(1,2-PHENYL-   ENE)-, -(1,4-PHENYLENE)-O-(1,4-PHENYLENE)-, -(1,4-   PHENYLENE)-CH2-(1,4-PHENYLENE)-, AND -(1,5-NAPHTHYLENE)-   PROVIDING THAT WHEN A IS A2, AT LEAST ONE OF SAID R1, R2, R3 AND R4 IS A SUBSTITUENT CONTAINING -SO3M, WHEREIN M IS THE SAME AS DEFINED ABOVE, AND A SILVER HALIDE PHOTOHALIDE PHOTOGRAPHIC EMULSION.

April 3, 1973 KEISUKE SHIBA ET Al. 3,725,074

FOGGED, DIRECT POSITIVE SILVER HALIDE EMULSIONS CONTAINING HYDROXYPHTHALEIN DYES AND SULFONATED COMPOUNDS Filed March 19, 1971 DENSITY (D) nel zo LOG E DENSITY (D) LOG E INVENTORS KEISUKE SHIBA MASANAO HINATA KDUTARO YAMASUE TOKIHARU KOIYDO BY Suff, 1MM' M' Zzww W ATTORNEYS United States Patent O 3,725,074 FOGGED, DIRECT POSITIVE SILVER HALIDE EMULSIUNS CONTAINING HYDROXYPHTHAL- EIN DYES AND SULFONATED COMPOUNDS Keisulre Shiha, Masanao Hinata, Koutaro Yamasne, and Tolriharu Kondo, Kanagawa, Japan, assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan Filed Mar. 19, 1971, Ser. No. 125,992 Claims priority, application Japan, Mar. 19, 1970,

Int. Cl. G03c 1/08 U.S. Cl. 96--122 14 Claims ABSTRACT 0F THE DISCLOSURE A direct positive silver halide photographic emulsion containing at least one dye represented by the general formula:

wherein X1, X2, X3, X4 and X5 each represents a halogen atom; m, n, L, `and p represent 0 or 1; q represents 0, 1, 2, 3 or 4; providing that when said m, n, L, p and q are 0, said X1, X2, X3, X4 and X5 each represents a hydrogen atom; and M represents a member selected from the group consisting of a hydrogen atom, an alkali metal atom, NH4, and an alkaline earth metal; together with at least one compound represented by the general in R4 wherein Y represents a member selected from the group consisting of =CH and =N--; R1, R2, R3, and R4 each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group, a halogen atom, a heterocyclic nucleus, an alkylthio group, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, a substituted alkylamino group, an arylamino group, a substituted arylamino group, a heterocyclylamino group, an aryl group and a mercapto group; and -A- represents at least one member defined as A1 and A2, said A1 being a member selected from the group consisting of:

SOaM SOaM 03M SOsM SOsM and SIOgM 3,725,074 Patented Apr. 3, 1973 wherein M represents a member selected from the group consisting of a hydrogen atom and a cation giving water solubility to said compound; and said A2 being a member selected from the group consistingI of:

and

providing that when A is A2, at least one of said R1, R2, R3 and R4 is a substitutent containing -SO3M, wherein M is the same as defined above; and a silver halide photohalide photographic emulsion.

BACKGROUND lOF THE INVENTION (l) Field of the invention This invention relates to a silver halide photographic emulsion and more particularly to a direct positive silver halide photographic emulsion.

(2) Description of prior art It is known that by incorporating a sensitizing dye in a silver halide photographic emulsion which has been preliminarily fogged and capable of directly providing a positive image by exposure and development, the silver halide is spectrally sensitized. It is also known that, depending upon the kind of sensitiziug dye employed and the amount of the sensitizing dye added to the emulsion, the contrast of the image obtained is varied.

In general, although by incorporating a sensitizing dye in a direct positive silver halide photographic emulsion the sensitivity thereof increases, it frequently happens that the maximum density (Dmax) is reduced and the contrast lowered, thus preventing suicient images from being obtained.

As a result of various studies, we have discovered that a halogen-substituted hydroxyphthalein dye represented by the following general Formula I is an excellent dye for maintaining the denite maximum density and definite contrast and increasing the sensitivity.

SOaM

SOsM

SOaM SOaM 3 General Formula I:

(Xm (X011 C/ (Xlr, l t 4) o o o- (X19q 2M+ wherein X1, X2, X3, X4, and X5 each represents a halogen atom; M represents a hydrogen atom, an alkali metal (such as Na or K), NH4, or an alkaline earth metal (such as ltCa); m, m, L, and p represent -0 or 1; q Irepresents 0, 1, 2, 3, or 4; said X1, X2, X3, X4, and X5 being a hydrogen atom when m, n, L, p, and q are 0.

On the other hand, when a sensitizing dye is incorporated in a direct positive silver halide photographic emulsion, the sensitivity thereof may increase. However, in some instances the `ao-called re-reversion becomes alkylthio group (such as a methylthio group or an ethylthio group), an arylthio group (such as a phenylthio group or a tolylthio group), an amino group, an alkylamino group or a substituted alkylamino group (such as a methylamino group, a dimethylamino group, a diethylamino group, a dodecylamino group, a cyclohexyl amino group, a -hydroxyethylamino group, a di-beta-hydroxyethylamino group, or a beta-sulfoethylamino group), an arylamino group or a substituted arylamino group (such as an anilino group, an o-sulfoanilino group, a m-sulfoanilino group, a p-sulfoanilino group, an o-anisylamino group, a m-anisylamino group, a p-anisylamino group, an o-toluidino group, a m-toluidino group, a p-toluidino group, an o-carboxyanillino group, a m-carboxyanilino group, a p-carboxyanilino group, a hydroxyanilino group, a naphthylamino group, or a sulfonaphthylamino group), a heterocyclylamino group (such as a Z-benzothiazoleamino group or a 2-pyridylamino group), an aryl group (such as a phenyl group) or a mercapto group; and --A- represents a member of A1- or A2- as shown below.

SOsM SO3M -Q-Q, Ce-- larger and sucient whiteness cannot be obtained. By the term re-reversion is meant the phenomenon that is shown by the dotted line of the curve in PIG. 1 of the accompanying drawings; after the density in the charaeteristic curve decreases, the density increases again.

The extent of the occurrence of the re-reversion depends upon the manner in which the silver halide photographic emulsions are prepared, but the occurrence of the phenomenon is particularly severe when a silver halide photographic emulsion is sensitized by the halogen-substituted hydroxyphthalein -dye represented by the abovementioned general Formula I and accordingly the practical use of the dye has been diicult.

SUMMARY TOP THE INVENTION It is therefore an object of this invention to provide a high-sensitive direct positive silver halide photographic emulsion which can maintain a definite maximum density and a high contrast, is not accompanied by re-reversion, and has a low minimum density.

The above object of this invention can be attained by incorporating a compound represented by the following general Formula II in a direct positive silver halide photographic emulsion sensitized by the halogen-substituted hydroxyphthalein dye represented by the general Formula i mentioned above.

'General Formula II wherein Y represents |=CH or =N-; R1, R2, R3, and R4 each represents a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group (such as a phenoxyl group, an o-toloxyl group, a p-sulfophenoxyl group or a meta-naphthoxyl group), a halogen atom (such as a chlorin@ atom or a bromne atom), a heterocyclic nucleus, an

wherein M represents a hydrogen atom or a cation giving water solubility to the compound; and

providing that when A is A2, at least one of said R1, R2, R3 and R4 is a substituent containing -SO3M, wherein M is the same as defined above.

'DETAILED DESCRIPTION OF THE INVENTION Practical examples of the compounds represented by the general Formula I mentioned above are shown below:

Compound I-l:

5 Compound I-2:

C1 $1 o Ho o m LCCI -C o H Compound I-3 BI :lf o N510 .-0

-CooNa Compound I-4:

B l I?!- 0 H O .-O

I- \C/ I I Compound I-5 if e 0 NaO ...0

C1 -COONa Compound I-6:

BI 131' No.0- /O O B r \C/ B r -C O 0 Na 6 Compound I-7 COOK Compound 1 8;

if e

O Nao O BI \C/ Br I COONa Compound 1 9;

I I O Nao- O I \C/ I I The dyes represented by the general Formula I mentioned above are commercially available materials and Well known.

The practical examples of the compounds represented by the general Formula II are shown Ibelow:

Compound lI-l ogN SOaNa Compound II-Z:

Compound II-3:

Compound II-4:

Compound II-S: @1D-NH H 1W N m IN mm N WIN N H N a m o IS H C H C u m O IS k H m m m NV W4 N IN I |I N Compound II-6:

Compound II-7:

Compound II-S:

Compound II-9:

SOaNa Compound II-10:

o 1.. 4 7 7, 3 9 .n 1 A d n u m. m C

Compound II-IZ Compound II-13:

N IN N m M Q o mw o. Q HV! N N\ \m #IIN N H Compound II14:

sosNa Compound II-15:

N 0i) EN@ HN Compound II-16: @SHN I NH@ NT3@ 1 1 Compound E[I-18:

SO aNiL \l/N soma,

Compound 1I-19:

SoaNa goaNa Compound ITI-20:

S O aNa @HNHMQQQWM Compound I'I-2l:

N HN m-HN--orr=on--NH I N soaNa soaNa Compound 11-22: @y o Compound II-23:

l N soaNa SOaNa SOaN SOgNa Compound lI-24z S O3Na S OsNa @3o-I NwN-HN-Q-CHZ-GHZQ-NH The direct positive silver halide photographic emulsion sensitized by the dye of general Formula l is such that the photographic emulsion has a high sensitivity without reducing the maximum density (Dmax) and contrast by the addition of the dye. However, because the direct positive silver halide photographic emulsion sensitized by the dye of general Formula I exhibits re-reversion severely and the minimum density (Dmm) is high, such a photographic emulsion has not been employed practically.

As a compound for reducing the formation of the re-reversion and also the minimum density, a densensitizing compound such as pinakryptol yellow is known to be eifective. However, when a desensitizing compound, such as pinakryptol yellow is incorporated in the direct positive silver halide photographic emulsion sensitized by the dye represented by the general Formula I, the Dmax is scarcely reduced. However, such an attempt is accompanied with the defect that the reversal sensitivity is reduced together with the reduction of the formation of the re-reversion and the minimum density.

However, when the compound represented by the general Formula II is present together with the dye represented by the general Formula I in the direct positive silver halide emulsion according to the present invention, the maximum density is scarcely reduced and the formation of the re-reversion and the minimum density is also reduced. In addition, the reversal sensitivity does not reduce, but in some cases increases.

While the pinakryptol yellow, etc., exhibits a desensitizing property to ordinary negative or positive photo- :graphic emulsions, the compound represented by the general Formula II has almost no desensitizing property to such photographic emulsions and has no influence thereon. Thus, it is surprising that when the compound of the general Formula II is used together with the dye represented by the general Formula I, the formation of the re-reversion and the minimum density are reduced.

It is usually profitable to add to a silver halide photographic emulsion the dye represented by the general Formula I and the compound represented by the general Formula II as a solution of each. As the solvent for the dye represented by general Formula I, there is water, methanol, and ethanol. As the solvent for the compound represented by general Formula II, there is water, methanol and ethanol and as occasion demands, an alkali, such as sodium hydroxide, may be added to the solvent.

The eifective amount of the dye shown by the general Formula II to be added to a direct positive silver halide photographic emulsion is 1-200 mg., and preferably 10- 100 mg., per kilogram of the emulsion. The eifective amount of the compound of general Formula II is 5-2,000 mg., and preferably -1,000 mg., per kilogram of the emulsion. The ratio of the compound of the general Formula I to the compound of the general Formula II is from 1/5 to l/50 by weight.

In the silver halide emulsion employed in this invention, a silver salt such as silver chloride, silver bromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide may be used.

The emulsiication and the physical ripening of the silver halide photographic emulsion used in this invention may be made in the manner conventionally employed for ordinary photographic emulsions, but a salt of the metal belonging to Group VIII of the Periodic Table, such as an iridium salt or rhodium salt may be added t0 the silver halide emulsion during the precipitation formation or during the physical ripening. The silver halide used in the present invention is fogged to the maximum density by light exposure or by a chemical fogging agent. The chemical fogging agent used for such purpose is required to fog the silver halide without imparting any deleterious effect to the silver halide emulsion, and usually thiourea dioxide, stannous chloride, formaldehyde or hydrazine is used. After the fogging operation is nished, the pH and PAg are controlled as the occasion demands.

A solution of the dye represented by the general Formula I is first added to a silver halide emulsion and then a solution of the compound represented by the general Formula H is added to the emulsion followed by stirring well. 'Ihe silver halide emulsion is applied to a support The solution of the dye represented by the general Formula II may be added prior to the addition of the solution of the compound shown by the general Formula I, or a mixture of them may be :added to the emulsion. Furthermore, these additives may be added to the silver halide emulsion during ripening after water Washing. Moreover, ordinary additives, such as a wetting agent or a hardening agent, may be added to the silver halide emulsion.

As the support, there may be employed a glass sheet, a cellulose derivative film, a synthetic resin film, a barytacoated paper, a waterproof paper, a laminated paper, etc.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing a characteristic curve of a known emulsion.

FIG. 2 is a graph showing a characteristic curve of the emulsion according to this invention.

A better understanding of the present invention will be attained from the following example which is merely illustrative and not limitative of the present invention.

EXAMPLE 1 A silver chloroiodo-bromide emulsion (containing 1.3 mol percent iodine and 21.3 mol percent bromine) was fogged by formalin and the pH and PAg were adjusted to 5.6 and 6.7 respectively. The dye represented by the general Formula I was added to the emulsion followed by stirring and then the compound represented by the general Formula II Was added thereto while the mixture was stirred sufciently. The silver halide emulsion thus prepared was applied to a triacetyl cellulose lm base. For the sake of comparison, a fogged silver halide photographic emulsion having the same composition as above to which, however, only the dye represented by the general Formula I had been added, was applied to the same kind of film base. After drying, each of the light-sensitive films thus prepared was exposed through a step wedge by means of a sensitometer and then developed in a developing solution having the following composition:

Water to make 1 liter.

The direct positive image obtained by the development was fixed by a fixing solution containing sodium thiosulfate, washed with water and dried. Thereafter, the optical density of the image was measured by means of a desensitometer. The re'sults are shown in Table 1.

DETAILED DESCRIPTION OF THE DRAWINGS The characteristic curves of a few samples in this example are shown in the graph of FIG. 2 and curves 2, 3 and 4 in FIG. 2 correspond to test numbers 9, l5 and 25, respectively. As is clear from these results, the reduction in sensitivity was observed in the sample containing pnakryptol yellow (pinakryptol yellow was added to the silver halide emulsion in place of the compound of the general Formula II, andthe results are shown as Test No. 25 in Table I-1 or the characteristic curve 4 in FIG. 2 for comparison.

Although the present invention has been suliciently described in the foregoing specification and example included therein, it is readily apparent that various changes and modilications may be made without departing from the scope thereof.

Whiteughn sensitivity (Relative Maximum Minimum value) (Dum.) (Dumm) consisting of a hydrogen atom, an alkali metal atom, NH4, and an alkaline earth metal; together with at least one compound represented by the general formula:

(II) N N 45 Rr( m-NH-A-NH- -Ra TABLE I Compound of Formula (I) Compound of Formula. (H) amount (mg./kg.emulsion) amount (1ng./kg.emu1sion) What we claim is: 1. A direct positive silver hahde photographic emuls1on having uniformly fogged silver hallde grains contaimng a sensitizing effective amount of at least one dye represented by the general formula Test No.

SOaM

I SOQM -Q-M-Q l S 03M SOxM providing that when A is A, at least one of said R1, R2, R3 and i114I is a substituent containing -SO3M, wherein M is the same as deined above,

said compound of Formula II ibeing present in an amount which will not decrease sensitvity.

2. The photographic emulsion of claim 1, wherein X1, X2, X3 and X4 in general Formula I represent a member selected from the group consisting of bromine and iodine, and R1, R2, Rs and `R4 in the general Formula II represent a member selected from the group consisting of an aryloxy group, an arylthio group, an arylamino group and a substituted arylamino group.

3. The photographic emulsion of claim 1, wherein the dye of general Formula I is a member selected from the group consisting of:

-OOONa Cl C1 o1 \C, o1 I -COOH llr llr 0 Neo o COONa lr llr O no -o -CO OH Br llr 0 NaO 0 C1 -COONa Br llr 0 NaO O Br \Cy Br -C OONa Br IIS: O Nao o Br \C/ Br C1 COOK Br l?! 0 NaO -0 Br \C/ -Br and and

4. The photographic emulsin of claim 3, wherein said dye is a member selected from the group consisting of COONa fl; y 5. The photographi,emulsio'nl'ofclaim 1, ,fwheljeiuthe 25 compound of the genelralfFormula-II-is awmember; se-

lected from the group consistingbof:

1;-, \/N soma goma I N HI SOaNa III( CHLOE):

l SOzNa l m@ f T s'oaNa slozNa N SOaNa NH-CHa SONa SOaNa 6. The photographic emulsion of` 5, wherein said compound is a member selected from `the group conf sisting of:

l. soaNa v ,somal .l N

@HNHNQSSHQM AWS@ Y l v NHN. gogh@ Slm .NH@-O.Qy.

S OaNa S OgNa 7. The photographic emulsionof claim 1, wherein the 10 amount of the dye represented by general Formula I is from 1 mg, to 200 mg. per kilogram of said silver halide emulsion. i,

8. The photographic emulsion of claim 1, wherein the amount of the compound represented by general Formula II is from 5 mg. to 2,000 mg. per kilogram of said silver halide emulsion. A

9. The photographic emulsion of claim 1, wherein the ratio of the compound of general Formula I to the compound of general Formula II to be added to the silver halide emulsion is from 1/5 to 1/50 by weight ratio.

10. A silver halide photographic element comprising a support and a layer of the direct positive silver halide emulsion of claim 1.

11. The photographic emulsion of claim 7, wherein 2 said dye is present in an amount of 10 mg. to 100 mg. per kilogram of said silver halide emulsion.

@when-@-N-NIINH..

12. The photographic emulsion of claim 8, wherein said compound is present in an amount of from 10 mg.

t to 1,000 mg. per kilogram of said silver halide emulsion.

UNITED STATES PATENTS 20 3,537,858 11/1970 Wise 96-107 2,323,187 6/ 1943 Arens et al. 96-64X NORMAN G. TORCHIN, Primary Examiner f W. H. LOUIE, IR., Assistant examiner. 5

U.S. Cl. X.R. 96-64, 107, 1'39 

